EP2934686B1 - Procédé de coloration respectueux des cheveux à prétraitement au silicone et préparation d'agent oxydant renfermant de l'huile - Google Patents

Procédé de coloration respectueux des cheveux à prétraitement au silicone et préparation d'agent oxydant renfermant de l'huile Download PDF

Info

Publication number
EP2934686B1
EP2934686B1 EP13792898.2A EP13792898A EP2934686B1 EP 2934686 B1 EP2934686 B1 EP 2934686B1 EP 13792898 A EP13792898 A EP 13792898A EP 2934686 B1 EP2934686 B1 EP 2934686B1
Authority
EP
European Patent Office
Prior art keywords
amino
hydroxyethyl
phenylenediamine
hair
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13792898.2A
Other languages
German (de)
English (en)
Other versions
EP2934686A2 (fr
Inventor
Matthias Schweinsberg
Jisook Baek
Astrid Kleen
Erik Schulze Zur Wiesche
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2934686A2 publication Critical patent/EP2934686A2/fr
Application granted granted Critical
Publication of EP2934686B1 publication Critical patent/EP2934686B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/884—Sequential application

Definitions

  • the present invention relates to a gentle process for oxidative hair coloring, in which keratinic fibers are protected from oxidative influences.
  • the oxidative dyeing of hair poses the problem that scalp irritation and damage to the keratin fiber may occur due to the aggressive agents.
  • the natural hydrophobicity of the keratinic fiber is reduced because the dyeing or whitening agents must first make the hair penetrable in order to develop their effect.
  • the water-repellent effect is on the one hand a natural protection of the hair, on the other hand, the consumer desired parameters such as shine, suppleness, grip and "falling" of the hair are closely linked to her.
  • pre-treatment agents are on the market, which should protect the hair from the aggressive influence.
  • these often complicate the hair or impair the success of the subsequent lightening or coloring of the hair; in particular, the washfastness of the dyeing may be degraded by the pretreatment agent.
  • a method should be provided in which the hair is not weighted and even with a not immediately before the oxidative dyeing pretreatment achieve the desired effect, whereby the time between pre-treatment and dyeing can be extended.
  • aminated silicones in hair care is state of the art. These are widely used in shampoos and especially in conditioners to develop nurturing effects there. So revealed the EP 1771144 B1 hair conditioning agents with amino-functional silicones. The agents described there are aftertreatment agents.
  • EP 1312334 B1 (Aminosilicone and thickener) as well EP 1312335 B1 (Aminosilicone and conditioner) disclose hair aftertreatment agents .. In the former document also extremely water rich formulations are disclosed.
  • Pre-treatment agents preferably used in accordance with the invention are characterized in that they contain 4-morpholinomethyl-substituted silicone (s) in a total amount of from 0.001 to 5% by weight, preferably 0.005 to 2% by weight, particularly preferably 0.01-1 Wt .-%, most preferably 0.02 - 0.1 wt .-%, each based on the total weight of the pretreatment agent.
  • s 4-morpholinomethyl-substituted silicone
  • Pre-treatment agents preferably used according to the invention are characterized in that they contain the at least one 4-morpholinomethyl-substituted silicone of the formula (V) in water emulsified form.
  • Pre-treatment agents used with particular preference contain 30-98% by weight, preferably 40-90% by weight, more preferably 50-85% by weight, most preferably 60-80% by weight of water, in each case based on the total weight of the pretreatment agent ,
  • Pre-treatment agents used with particular preference are in the form of an oil-in-water emulsion in which the number-average size of the silicone particles in the emulsion is in the range from 3 to 500 nm, preferably in the range from 5 to 60 nm.
  • the structural units of the formulas (I), (II), (IIIa), (IIIb), (IIIe) and (IIIf) can be present randomly distributed in the molecule, but the silicones used according to the invention can also be block copolymers of blocks of the individual structural units, again, the blocks may be statistically distributed.
  • the * at the free valences of the structural units (I), (II), (IIIa), (IIIb), (IIIe) or (IIIf) stands for a bond to one of the structural units (I), (II), (IIIa ), (IIIb), (IIIe) or (IIIf) or for an end group B (Si-bonded) or D (O-bonded).
  • A is the half of a connecting O atom in a structure unit (III).
  • A is -OH.
  • the structural units of the formulas (I), (II), (IIIa), (IIIb), (IIIe) and (IIIf) can preferably be randomly distributed.
  • Structural formula (V) is intended to make it clear that the siloxane groups n and o do not necessarily have to be bound directly to an end grouping B or D, respectively. Rather, in preferred formulas (V) a> 0 or b> 0 and in particularly preferred formulas (V) a> 0 and b> 0, i. the terminal moiety B or D is preferably linked to a dimethylsiloxy moiety. Also in formula (V), the siloxane units a, b, c, n and o are preferably randomly distributed.
  • the silicones used according to the invention represented by formula (V) may be bilateral
  • formula (V ) is thus specified to one of the formulas (Va), (Vb), (Ve) or (Vf):
  • pretreatment agents containing a 4-morpholinomethyl-substituted silicone in which more than 50 mol% of the structural units are dimethylsiloxy units are preferred for the process according to the invention are, ie in which the structural unit (I) makes up at least half of all the structural units of the silicone used.
  • silicones are preferred in which m> (n + o) or (a + b + c)> (n + o).
  • Still further preferred pretreatment agents used in the present invention include a 4-morpholinomethyl substituted silicone in which more than 87.5 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) makes up more than 875 thousandths of all the structural units of the silicone used.
  • silicones are preferred in which m> 8 (n + o) or (a + b + c)> 8 (n + o).
  • Still further preferred pretreatment agents used in the present invention include a 4-morpholinomethyl substituted silicone in which more than 96 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) is at least ninety-six hundredths of all the structural units of the silicone used.
  • silicones are preferred in which m> 25 (n + o) or (a + b + c)> 25 (n + o).
  • Still further preferred pretreatment agents used in the present invention include a 4-morpholinomethyl substituted silicone in which more than 98.7 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) comprises at least nine hundred and seventy-seven thousandths of all the structural units of the silicone used.
  • silicones are preferred in which m> 77 (n + o) or (a + b + c)> 77 (n + o).
  • Still further preferred pretreatment agents used in the present invention include a 4-morpholinomethyl substituted silicone in which more than 99.5 mole percent of the structural units are dimethylsiloxy units, i. in which the structural unit (I) is at least nine hundred and ninety-five thousandths of all the structural units of the silicone used.
  • the pretreatment agent used in step a contains hydroxy-terminated (s) 4-morpholinomethyl-substituted silicone (s) in which the molar ratio hydroxy / alkoxy in the range from 0 , 2: 1 to 0.4: 1, preferably in the range of 1: 0.8 to 1: 1.1.
  • Another method preferred according to the invention is characterized in that weight-average molar mass of the 4-morpholinomethyl-substituted silicone of the formula (V) used in step a is in the range from 2,000 to 1,000,000 gmol -1 , preferably in the range from 5,000 to 200,000 gmol -1 .
  • the average molar masses of amino-substituted silicones can be measured, for example, by gel permeation chromatography (GPC) at room temperature in polystyrene.
  • GPC gel permeation chromatography
  • columns Styragel columns ⁇ , as eluent THF and as flow rate 1 ml / min can be selected.
  • the detection is preferably carried out by means of refractometry and UV meter.
  • Belsil ADM 8301 E Ex Wacker Silicones
  • Belsil ADM 8301 E is a microemulsion and consists of the following constituents: amodimethicone / morpholinomethyl silsesquioxane (10% by weight); Trideceth-5 (5 wt%); Glycerin (2.5% by weight), phenoxyethanol (0.45% by weight) and water (82.05% by weight):
  • nonionic components are likewise present in the pretreatment agents used according to the invention.
  • these nonionic components have positive effects on the storage stability of the pretreatment agent used in the invention.
  • Nonionic components which are particularly useful herein are ethoxylates of decanol, undecanol, dodecanol, tridecanol, myristyl alcohol, cetyl alcohol and / or stearyl alcohol.
  • Particularly suitable ethoxylated tridecanols have proven to be incorporated with particular preference in the pretreatment agent used in the invention.
  • Pre-treatment agents used particularly preferably according to the invention contain-in each case based on their weight-0.001 to 5% by weight, preferably 0.005 to 3.5% by weight, particularly preferably 0.01 to 2% by weight, more preferably 0.05.
  • Pre-treatment agents preferably used according to the invention comprise, based on the total weight of the composition, from 0.001 to at most 6% by weight of surfactant (s), the abovementioned ethoxylates of decanol, undecanol, dodecanol, tridecanol, myristyl alcohol, cetyl alcohol and / or stearyl alcohol being included.
  • surfactant s
  • the pretreatment agents used according to the invention are preferably formulated with low viscosity, that is to say with a viscosity (measured at 20 ° C.) in the range of 10-2000 mPas, preferably 20-1000 mPas, particularly preferably 50-800 mPas. It has also been shown that thickening polymers can attenuate the effect according to the invention, so that preferred pretreatment agents used according to the invention are characterized in that they contain thickening polymers in a total amount of ⁇ 2.5% by weight, preferably ⁇ 1% by weight. , further preferably ⁇ 0.5 wt .-% and in particular ⁇ 0.01 wt .-%, each based on the weight of the pretreatment agent.
  • the pretreatment agents used according to the invention may contain further ingredients. Preference is given here to the use of polyhydric alcohols which have moisturizing properties.
  • Pre-treatment agents used according to the invention which are preferred are at least one polyhydric alcohol, preferably selected from the group of sorbitol and / or glycerol and / or 1,2-propylene glycol or mixtures thereof, in a total amount of 0.05-15% by weight 0.1 - 10 wt .-%, particularly preferably 0.15 - 5 wt .-% and in particular 0.15 - 1 wt .-%, each based on the weight of the pretreatment agent. For certain applications, it may be advantageous to use only one of the three preferred polyhydric alcohols mentioned above.
  • glycerin is preferred. However, in other applications, mixtures of two of the three polyhydric alcohols or all three polyhydric alcohols may be preferred. Particularly advantageous here is a mixture of glycerol, sorbitol and 1,2-propylene glycol in a weight ratio of 1: (0.5-1): (0.1-0.5) has been found.
  • glycerol and 1,2-propylene glycol are suitable as further polyhydric alcohols are those having at least 2 OH groups, preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and mixtures thereof. Among these compounds, those having 2 to 12 OH groups, and especially those having 2, 3, 4, 5, 6 or 10 OH groups are preferred.
  • the (n, n + 1) or (n, n + 2) diols with non-terminal OH groups can also be used.
  • Important representatives of polyhydroxy compounds having 2 OH groups are also the polyethylene and polypropylene glycols.
  • polyhydric alcohols may, for.
  • propylene glycols polyethylene glycols, especially those having average molecular weights of 200-800, are used.
  • Particularly preferred is the use of glycerol, so that agents which contain no other polyhydric alcohols other than glycerol are particularly preferred.
  • the use of certain care substances in the pretreatment compositions of the process according to the invention is preferred.
  • the pretreatment agents used according to the invention may with particular preference contain one or more amino acids.
  • Amino acids which can be used particularly preferably according to the invention are selected from the group glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, proline, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, cysteine, methionine, lysine, arginine, histidine, ⁇ Alanine, 4-aminobutyric acid (GABA), betaine, L-cystine (L-Cyss), L-carnitine, L-citrulline, L-theanine, 3 ', 4'-dihydroxy-L-phenylalanine (L-dopa), 5'-hydroxy-L-tryptophan, L-homocysteine, S-methyl-L-methionine, S- ally
  • Preferred pretreatment agents used according to the invention comprise one or more amino acids in narrower ranges.
  • pretreatment agents used according to the invention are characterized in that they have a care substance of 0.01 to 5 wt .-%, preferably 0.02 to 2.5 wt .-%, particularly preferably 0.05 to 1.5 wt .-%, further preferably 0.075 to 1 wt .-% and in particular 0.1 to 0.25 wt .-% amino acid (s), preferably from the group glycine and / or alanine and / or valine and / or lysine and / or leucine and / or Threonine, each based on the total weight of the pretreatment agent.
  • the pretreatment agent used according to the invention may be formulated as a low-viscous water-based emulsion, as a spray, as a cream, gel, lotion, paste, shampoo or conditioner.
  • the method according to the invention comprises the application of a pretreatment agent to keratinic fibers and an oxidative dyeing treatment following this within a period of one second to 24 hours.
  • a great advantage of the pretreatment agents used in step a) is that they are not only effective if they are applied immediately before the oxidative dyeing treatment, but can be applied up to 24 hours in advance without a weakening of the effect due to external influences to be feared. In this way it is possible, for example in the morning after shampooing to carry out step a) of the method according to the invention and the oxidative dyeing treatment only in the evening.
  • Preferred processes according to the invention are characterized in that the time between process steps a and b is from 2 seconds to 20 minutes, preferably from 30 seconds to 10 minutes, more preferably from 1 to 5 minutes.
  • process step a is allowed to act on the hair for a period of 2 seconds to 120 minutes, preferably 5 seconds to 10 minutes, before process step b takes place.
  • the drying process is preferably carried out at a temperature of 20 ° C to 150 ° C.
  • the drying process or the drying processes is particularly preferably preceded by no rinsing of the hair.
  • a preferred method according to the invention is therefore characterized in that no rinsing of the hair takes place between the application of the pretreatment agent and the drying process or the drying processes carried out in process step a.
  • step b) comprises applying a hair colorant comprising a composition (B) comprising at least one composition (B) comprising at least one developer type oxidation dye precursor and at least one coupler type oxidation dye precursor an oxidizing agent, wherein the composition (B) contains at least one cosmetic oil in a total amount of 10 to 80% by weight based on the weight of the composition (B).
  • the composition (B) used in the method according to the invention contains as the first compulsory ingredient at least one oxidizing agent.
  • Preferred oxidizing agents are selected from peroxo compounds, preferably selected from hydrogen peroxide, solid addition compound of hydrogen peroxide to inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H 2 O 2 (n is a positive integer greater than 0), urea peroxide and Melamine peroxide, further selected from diammonium peroxodisulfate (also referred to as ammonium persulfate), disodium peroxodisulfate (also referred to as sodium persulfate) and dipotassium peroxodisulfate (also referred to as potassium persulfate) and mixtures of these oxidants.
  • diammonium peroxodisulfate also referred to as ammonium persulfate
  • Oxidants which are very particularly preferably used according to the invention are aqueous hydrogen peroxide solutions.
  • concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; Preferably, 6-12% by weight solutions in water are used.
  • the composition used (B) - based on their weight - 1 to 24 wt .-%, preferably 4 - 10 wt .-%, particularly preferably 3-6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ).
  • a dyeing composition which contains one or more oxidation dye precursors and optionally one or more substantive dyes is usually mixed with an aqueous oxidizing agent-containing composition to form an application-ready hair dye and then applied to the hair shortly before application to the hair.
  • Most of the dyeing composition and the oxidizing agent-containing composition are coordinated so that at a mixing ratio of 1 to 1, based on parts by weight, in the hair dye, an initial concentration of hydrogen peroxide of 0.5 to 12 wt .-%, preferably 2 to 10 wt. -%, more preferably 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H 2 O 2 ) based on the weight of the hair dye is present.
  • the concentrations required in the ready-to-use dyeing agent result from mixing ratios other than 1: 1, for example by a weight-related mixing ratio of 1: 2 or 1: 3 or even 2: 3.
  • Preferred processes according to the invention are characterized in that the ready-for-use hair dye used in process step b) has an initial amount of hydrogen peroxide of 0.5-12% by weight, preferably 2-10% by weight, particularly preferably 3-6% by weight of hydrogen peroxide (calculated as 100% H 2 O 2 ) based on the weight of the hair dye contains.
  • the ready-for-use hair dye employed in process step b) comprises at least one cosmetic oil in a total amount of 5 to 50% by weight, preferably 8 to 40% by weight, more preferably 12 to 30% by weight. , most preferably 15-25 wt .-%, in each case based on the weight of the hair dye.
  • the pH of the ready-to-apply hair dye used in step b) is in the range of 7 and 11, in particular in the range of 8 and 10.5.
  • the pH values are pH values which were measured at a temperature of 22 ° C.
  • the alkalizing agents which can be used according to the invention for adjusting the preferred pH can be selected from the group of ammonia, basic amino acids, alkali metal hydroxides, alkanolamines, alkali metal metasilicates, alkali metal phosphates and alkali metal hydrogenphosphates.
  • the alkali metal ions used are preferably lithium, sodium, potassium, in particular sodium or potassium.
  • the basic amino acids which can be used as alkalizing agents are preferably selected from the group consisting of L-arginine, D-arginine, D, L-arginine, L-lysine, D-lysine, D, L-lysine, particularly preferably L-arginine, D-arginine, D, L-arginine used as an alkalizing agent according to the invention.
  • alkali metal hydroxides which can be used as alkalizing agents are preferably selected from the group consisting of sodium hydroxide and potassium hydroxide.
  • alkanolamines which can be used as alkalizing agents are preferably selected from primary amines having a C 2 -C 6 -alkyl basic body which carries at least one hydroxyl group.
  • Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 -Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol , 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol.
  • Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol.
  • the use of hydrogen peroxide or its addition products to organic or inorganic compounds is often not sufficient.
  • a combination of hydrogen peroxide and Peroxodisulfatsalzen (persulfate salts) is usually used.
  • Preferred persulfate salts are ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, and mixtures thereof.
  • the at least one persulfate salt is preferably contained in a total amount of 0.1 to 25 wt .-%, particularly preferably in a total amount of 1 to 15 wt .-%, based on the weight of the ready colorant.
  • the composition (B) used in the invention contains at least one cosmetic oil in a total amount of 10 to 80% by weight, based on the weight of the composition (B).
  • the cosmetic oil is liquid under normal conditions (20 ° C, 1013.25 mbar); essential oils and perfume oils or fragrances are not counted among the cosmetic oils. Under normal conditions liquid cosmetic oils are immiscible with water.
  • Essential oils according to the invention are understood to mean mixtures of volatile components which are prepared by steam distillation from vegetable raw materials, such as. B. citrus oils. As far as in the present application of a cosmetic oil is mentioned, this is always a cosmetic oil that is not a fragrance and no essential oil, is liquid under normal conditions and immiscible with water.
  • a fragrance in the sense of the present application is in accordance with the expert definition as it can be found in the R ⁇ MPP Chemie Lexikon, as of December 2007. Thereafter, a fragrance is a chemical compound with odor and / or taste that excites the hair cell receptors of the olfactory system (adequate stimulus).
  • the necessary physical and chemical properties are a low molecular weight of at most 300 g / mol, a high vapor pressure, minimal water and high lipid solubility and weak polarity and the presence of at least one osmophoric group in the molecule.
  • fragrances according to the invention have a molecular weight of 74 to 300 g / mol, contain at least one osmophoric group in the molecule and have a smell and / or taste, that is, they excite the hair cell receptors of the olfactory system.
  • preferred cosmetic oils are selected from natural and synthetic hydrocarbons, particularly preferably of paraffin oils, C 18 -C 30 isoparaffins, in particular isoeicosane, polyisobutenes and polydecenes, for example, under the designation Emery ® 3004, 3006, 3010 or under the name Ethylflo ® ® from Albemarle or Nexbase 2004G from Nestle are available, further selected from C 8 -C 16 isoparaffins, in particular isododecane, isododecane, isotetradecane, and isohexadecane and mixtures thereof, and 1,3-di- (2-ethylhexyl) -cyclohexane (available, for. example, under the trade name Cetiol ® S from BASF).
  • C 18 -C 30 isoparaffins in particular isoeicosane, polyisobutenes and polydecenes
  • Further inventively preferred cosmetic oils are selected from the benzoic acid esters of linear or branched C 8-22 -alkanols. Particularly preferred are benzoic C12-C15 alkyl esters, z. B. available as a commercial product Finsolv ® TN, benzoic acid isostearyl, z. B. available as a commercial product Finsolv ® SB, ethylhexyl benzoate, z. B. available as a commercial product Finsolv ® EB, and Benzoeklatoneoctyldocecylester, z. B. available as a commercial product Finsolv ® BOD.
  • benzoic C12-C15 alkyl esters z. B. available as a commercial product Finsolv ® TN
  • benzoic acid isostearyl z. B. available as a commercial product Finsolv ® SB
  • ethylhexyl benzoate z. B. available as a commercial product Finsolv ® EB
  • Further inventively preferred cosmetic oils are selected from fatty alcohols having 6 to 30 carbon atoms, which are unsaturated or branched and saturated or branched and unsaturated.
  • the branched alcohols are also often referred to as Guerbet alcohols, since they are obtainable by the Guerbet reaction.
  • Preferred oils are alcohol 2-hexyldecanol (Eutanol ® G 16) 2-octyldodecanol (Eutanol ® G), 2-ethylhexyl alcohol and isostearyl alcohol.
  • More preferred cosmetic oils are chosen from mixtures of Guerbet alcohols and Guerbet alcohol esters, for example the commercial product Cetiol ® PGL (2-hexyldecanol and 2-hexyldecyl).
  • Particularly preferred may be the use of natural oils, eg, amaranth seed oil, apricot kernel oil, argan oil, avocado oil, babassu oil, cottonseed oil, borage seed oil, camelina oil, thistle oil, peanut oil, pomegranate seed oil, grapefruit seed oil, hemp oil, hazelnut oil, elderflower seed oil, currant seed oil, jojoba oil, linseed oil, macadamia nut oil, corn oil, almond oil , Marula oil, evening primrose oil, olive oil, palm oil, palm kernel oil, Brazil nut oil, pecan oil, peach kernel rapeseed oil, castor oil, sea buckthorn oil, sea buckthorn seed oil, sesame oil, soybean oil, sunflower oil, grape seed oil, walnut oil, wild
  • Further cosmetic oils which are particularly preferred according to the invention are selected from the dicarboxylic acid esters of linear or branched C 2 -C 10 -alkaholes, in particular diisopropyl adipate, Di-n-butyl adipate, di- (2-ethylhexyl) adipate, dioctyl adipate, diethyl / di-n-butyl / dioctyl sebacate, diisopropyl sebacate, dioctyl malate, dioctyl maleate, dicaprylyl maleate, diisooctyl succinate, di-2-ethylhexyl succinate and di (2 -hexyldecyl) succinate.
  • diisopropyl adipate Di-n-butyl adipate, di- (2-ethylhexyl) adipate, dioctyl adipate, diethy
  • Further cosmetic oils which are particularly preferred according to the invention are selected from the esters of linear or branched saturated or unsaturated fatty alcohols having 2 to 30 carbon atoms with linear or branched saturated or unsaturated fatty acids having 2 to 30 carbon atoms which may be hydroxylated.
  • These include 2-hexyldecyl stearate (Eutanol ® G 16 S), 2-hexyldecyl laurate, isodecyl neopentanoate, isononyl isononanoate, 2-ethylhexyl palmitate (Cegesoft ® C 24) and 2-ethylhexyl stearate (Cetiol ® 868).
  • cosmetic oils are selected from the addition products of 1 to 5 propylene oxide units of mono- or polyhydric C 8-22 alkanols, such as octanol, decanol, decanediol, lauryl alcohol, myristyl alcohol and stearyl alcohol, eg. B. PPG-2 myristyl ether and PPG-3 myristyl ether (Witconol APM ®).
  • propylene oxide units of mono- or polyhydric C 8-22 alkanols such as octanol, decanol, decanediol, lauryl alcohol, myristyl alcohol and stearyl alcohol, eg. B. PPG-2 myristyl ether and PPG-3 myristyl ether (Witconol APM ®).
  • Further inventively preferred cosmetic oils are selected from the addition products of at least 6 ethylene oxide and / or propylene oxide units of mono- or polyhydric C 3-22 alkanols such as glycerol, butanol, butanediol, myristyl alcohol and stearyl alcohol, which may be esterified if desired, for , As PPG-14 butyl ether (Ucon Fluid ® AP), PPG-9-butyl ether (Breox B25 ®), PPG-10 butanediol (Macol ® 57), PPG-15 stearyl ether (Arlamol ® E), and Glycereth-7 -diisononanoat.
  • PPG-14 butyl ether Ucon Fluid ® AP
  • PPG-9-butyl ether Breox B25 ®
  • PPG-10 butanediol Macol ® 57
  • PPG-15 stearyl ether Arlamol ® E
  • compositions selected from the C 8 -C 22 fatty alcohol esters of monohydric or polyhydric C 2 -C 7 hydroxycarboxylic acids, in particular the esters of glycolic acid, lactic acid, malic acid, tartaric acid, citric acid and salicylic acid.
  • esters based on linear C 14/15 alkanols, eg. B.
  • C 12 -C 15 alkyl lactate, and branched in the 2-position C 12/13 alkanols can be obtained under the trademark Cosmacol ® by the company Nordmann, Rassmann GmbH & Co, Hamburg, in particular the commercial products Cosmacol ® ESI , Cosmacol® ® EMI and Cosmacol® ® EIT.
  • cosmetic oils according to the invention are selected from the symmetrical, unsymmetrical or cyclic esters of carbonic acid with C 3-22 -alkanols, C 3-22 -alkanediols or C 3-22 -alkanetriols, eg. B. Dicaprylylcarbonat (Cetiol ® CC) or the esters according to the teaching of DE 19756454 A1 , in particular glycerin carbonate.
  • cosmetic oils which may be preferred according to the invention are selected from the esters of dimers of unsaturated C 12 -C 22 -fatty acids (dimer fatty acids) with monovalent linear, branched or cyclic C 2 -C 18 -alkanols or with polyvalent linear or branched C 2 -C 6 -alkanols.
  • dialkyl and alkylaryl such as cyclopentasiloxane, cyclohexasiloxane, dimethylpolysiloxane and Methylphenylpolysilöxan, but also include hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane.
  • Preferred may be volatile silicone oils, which may be cyclic, such as.
  • octamethylcyclotetrasiloxane for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane and mixtures thereof, as described for. B. in the commercial products DC 244, 245, 344 and 345 of Dow Corning.
  • suitable volatile linear silicone oils in particular hexamethyldisiloxane (L 2 ), octamethyltrisiloxane (L 3 ), decamethyltetrasiloxane (L 4 ) as well as any mixtures of two and three of L 2 , L 3 and / or L 4 , preferably mixtures such as those described, for example , B.
  • nonvolatile silicone oils are selected from higher molecular weight linear dimethylpolysiloxanes, commercially available e.g. Dow Corning® 190, Dow Corning® 200 fluid having kinematic viscosities (25 ° C) in the range of 5-100 cSt, preferably 5-50 cSt or even 5-10 cSt, and dimethylpolysiloxane having a kinematic viscosity (e.g. 25 ° C) of about 350 cSt.
  • compositions (B) used according to the invention are characterized in that the cosmetic oil is selected from natural and synthetic hydrocarbons, particularly preferably from paraffin oils, C 18 -C 30 isoparaffins, in particular isoeicosane, polyisobutenes and polydecenes, C 8 -C 16 -siloparaffins ', and 1,3-di (2-ethylhexyl) cyclohexane; the benzoic acid esters of linear or branched C 8-22 alkanols; Fatty alcohols having 6 to 30 carbon atoms which are unsaturated or branched and saturated or branched and unsaturated; Triglycerides of linear or branched, saturated or unsaturated, optionally hydroxylated C 8-30 fatty acids, in particular natural oils; the dicarboxylic acid esters of linear or branched C 2 -C 10 -alkanols; the esters of linear or branched saturated or unsaturated fatty alcohols having from 2
  • composition (B) used according to the invention comprises at least one cosmetic oil in a total amount of 12-70% by weight, preferably 14-60% by weight, more preferably 15-52% by weight and extraordinarily preferably 17-35 wt.%, in each case based on the weight of the composition (B).
  • Further preferred processes according to the invention are characterized in that the composition (B) used according to the invention contains at least one surfactant.
  • Suitable surfactants according to the invention it is particularly preferred to use a mixture of surfactants in order to optimally adjust the stability of the oxidizing agent compositions (B) used according to the invention.
  • the surfactant contained in the composition (B) is selected from nonionic surfactants and anionic surfactants as well as mixtures thereof.
  • Particularly preferably used nonionic surfactants are selected from with 20 to 100 moles of ethylene oxide per mole of ethoxylated castor oil, ethoxylated C 8 -C 24 -alkanols with 10 to 100 moles of ethylene oxide per mole, ethoxylated C 8 -C 24 -carboxylic acids of 10 to 100 moles Ethylene oxide per mole, with 20-100 moles of ethylene oxide per mole of ethoxylated sorbitan monoesters of linear saturated and unsaturated C 12 -C 30 carboxylic acids which may be hydroxylated, in particular those of myristic, palmitic, stearic or mixtures of these fatty acids, alkylmono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl
  • the ethoxylated C 8 -C 24 -alkanols have the formula R 1 O (CH 2 CH 2 O) n H, where R 1 is a linear or branched alkyl and / or alkenyl radical having 8-24 carbon atoms and n, the middle one Number of ethylene oxide units per molecule, for numbers from 10 to 100, preferably 10 to 30, particularly preferably 15 to 25 moles of ethylene oxide to 1 mole of caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, Isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical mixtures thereof.
  • adducts of 10-100 moles of ethylene oxide with technical fatty alcohols having 12-18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol are suitable.
  • Particularly preferred are laureth-10, laureth-12, laureth-15, laureth-20, laureth-30, myreth-10, myreth-12, myreth-15, myreth-20, myreth-30, ceteth-10, ceteth-12 , Ceteth-15, Ceteth-20, Ceteth-30, Steareth-10, Steareth-12 Steareth-15, Steareth-20, Steareth-30, Oleth-10, Oleth-12, Oleth-15, Oleth-20, Oleth- 30, ceteareth-10, ceteareth-15, ceteareth-12, ceteareth-15, ceteareth-20, ceteareth-30 and coceth-10, coceth-12, coceth-15, coceth-20 and coceth-30.
  • the ethoxylated C 8 -C 24 carboxylic acids have the formula R 1 O (CH 2 CH 2 O) n H, where R 1 O is a linear or branched saturated or unsaturated acyl radical having 8-24 carbon atoms and n, the average number of ethylene oxide units per molecule, for numbers from 10 to 100, preferably 10 to 30, moles of ethylene oxide to 1 mole of caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, cetylic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid , Arachic acid, gadoleic acid, behenic acid, erucic acid and brassidic acid and their technical mixtures.
  • Adducts of 10 to 100 moles of ethylene oxide with technical fatty acids containing 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty acid, are also suitable. Particularly preferred are PEG-50 monostearate, PEG-100 monostearate, PEG-50 monooleate, PEG-100 monooleate, PEG-50 monolaurate and PEG-100 monolaurate.
  • Preferred ones with 20-100 moles of ethylene oxide per mole of ethoxylated sorbitan monoesters of linear saturated and unsaturated C 12 -C 30 carboxylic acids which may be hydroxylated are selected from Polysorbate-20, Polysorbate-40, Polysorbate-60 and Polysorbate-80.
  • C 8 - C 22 alkyl mono- and oligoglycosides employed.
  • C 8 -C 22 -Aikyimono- and -oligoglycosides are known, commercially available surfactants and emulsifiers. Their preparation is carried out in particular by reacting glucose or oligosaccharides with primary alcohols having 8-22 carbon atoms.
  • the glycoside radical it is true that both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of up to about 8, preferably 1 -2, are suitable.
  • the degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products. Products which are obtainable under the trademark Plantacare ®, a glucosidically bonded C 8 -C 16 alkyl group containing at an oligoglucoside whose average degree of oligomerization at 1-2, in particular 1.2 to 1.4, is located.
  • Particularly preferred C 8 -C 22 alkyl mono- and oligoglycosides are selected from octyl glucoside, decyl glucoside, lauryl glucoside, palmityl glucoside, isostearyl glucoside, stearyl glucoside, arachidyl glucoside and behenyl glucoside and mixtures thereof.
  • the glucamine-derived acylglucamides are also suitable as non-ionic oil-in-water emulsifiers.
  • Suitable anionic surfactants in the compositions (B) used according to the invention are all anionic surfactants suitable for use in the human body which have a water-solubilizing, anionic group, for example a carboxylate, sulfate, sulfonate or phosphate group, and have lipophilic alkyl group having about 8 to 30 carbon atoms, preferably 8 to 24 carbon atoms in the molecule.
  • anionic group for example a carboxylate, sulfate, sulfonate or phosphate group
  • lipophilic alkyl group having about 8 to 30 carbon atoms, preferably 8 to 24 carbon atoms in the molecule.
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms ( Soaps), polyethoxylated ethercarboxylic acids, acylsarcosides, acyltaurides, acylisethionates, sulfosuccinic mono- and dialkyl esters and sulfosuccinic acid mono-alkylpolyoxyethyl esters having 1 to 6 ethylene oxide groups, linear alkanesulfonates, linear alpha-olefinsulfonates, sulfonates of unsaturated fatty acids having up to 6 double bonds, alpha-sulfofatty acid methyl ester of fatty acids, C 8 -C 20 -alkyl sulfates and C 8 --
  • Preferred anionic surfactants are soaps, C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl ether sulfates and C 8 -C 20 -Ethercarbon Acid having 8 to 20 carbon atoms in the alkyl group and up to 12 ethylene oxide groups in the molecule. Particularly preferred is sodium cetearyl sulfate.
  • the total amount of at least one surfactant in the oxidizing agent composition (B) is preferably from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight and more preferably from 1 to 2% by weight, based in each case on the total weight the oxidizer composition (B).
  • the oxidizing agent composition (B) used according to the invention particularly preferably contains a total of from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight and particularly preferably from 1 to 2% by weight, based in each case on the total weight of the oxidizing agent composition ( B), a mixture of nonionic and anionic surfactants.
  • composition (B) used according to the invention comprises at least one linear saturated alkanol having 12-30 carbon atoms.
  • Preferred linear saturated alkanols having 12-30 carbon atoms, in particular 16-22 carbon atoms are selected from cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol and mixtures of these alkanols.
  • Alkanol mixtures which are particularly preferred according to the invention are those obtainable in the industrial hydrogenation of vegetable and animal fatty acids.
  • the total amount of at least one linear saturated alkanol having 12 to 30 carbon atoms in the oxidizing agent composition (B) is preferably 0.1 to 10% by weight, preferably 0.5 to 7% by weight and more preferably 3 to 5% by weight. %, in each case based on the total weight of the oxidizing agent composition (B).
  • oxidation dye precursors can be divided into two categories, so-called developer components and coupler components.
  • Coupler components do not form significant staining in the course of oxidative staining alone, but always require the presence of developer components. Developer components can form the actual dye with themselves.
  • the developer and coupler components are usually used in free form. In the case of substances having amino groups, however, it may be preferable to use them in salt form, in particular in the form of the hydrochlorides or hydrobromides or of the sulfates.
  • Particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine , N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl ) propyl] amine, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxybenzyl) 5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N
  • Very particularly preferred developer components are selected from 4,5-diamino-1- (2-hydroxyethyl) pyrazole, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4 -Amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and mixtures of these compounds and their physiologically acceptable salts.
  • Extraordinary preference is given to 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its physiologically tolerated salts.
  • the developer components are preferably used in a total amount of from 0.01 to 20% by weight, more preferably from 0.2 to 10% by weight, and most preferably from 0.6 to 5% by weight, based on the weight of the composition (A), used.
  • the developer components are preferably in a total amount of 0.005 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-%, and most preferably 0.3 to 2.5 wt .-%, each based on the weight of the ready for use Colorant, used.
  • ready-to-use colorant is understood to mean the mixture of all oxidation dye precursors and all oxidizing agents, if appropriate in combination with a suitable cosmetic carrier, for example a cream base, and optionally in combination with at least one substantive dye.
  • Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component.
  • Couplers are preferably cyclic compounds which carry at least two groups on the cycle, selected from (i) optionally substituted amino groups and / or (ii) hydroxyl groups.
  • the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.
  • the at least one coupler component is preferably in a total amount of 0.01 to 20 wt .-%, particularly preferably 0.2 to 10 wt .-%, and most preferably 0.6 to 5 wt .-%, each based on the weight the composition (A) used.
  • the at least one coupler component is preferably used in a total amount of 0.005-10 wt%, preferably 0.1-5 wt%, and most preferably 0.3-2.5 wt%, each based on the weight of ready for use Oxidationsfärbeschs used.
  • Particularly preferred according to the invention are the combinations 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol and p-toluenediamine / 3-aminophenol.
  • the combination is 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol.
  • the agents used in step b) of this variant of the method according to the invention may additionally contain at least one substantive dye.
  • These are dyes that raise directly on the hair and do not require an oxidative process to form the color.
  • Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • a further preferred process according to the invention is characterized in that the dyeing agent applied in step b is rinsed off the fibers after a time of 5-60 minutes, preferably 30-45 minutes.
  • the colorant used in the process according to the invention in step b is from a Two component agent prepared, wherein one component, namely the composition (A), the oxidation dye precursors and the other component, namely the composition (B), the one or more oxidizing agents.
  • the ready-for-use colorant for step b is then prepared by mixing both components directly before the application step b. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or to be feared.
  • Hair strands were immersed for one minute in an aqueous emulsion of 4-morpholinomethyl-substituted silicone of formula (V) containing 0.01% by weight of 4-morpholinomethyl-substituted silicone (s) of formula (V) and 0.005 wt .-% branched trideceth-5, further contained 0.006 wt .-% glycerol and water ad 100 wt .-%, immersed and then dry-blown.
  • Dye cream in% by weight: Toluene-2,5-diamines sulfates 0.02 2-amino-4-hydroxyethylaminoanisole sulfates (1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzenesulfate) 0.02 4-amino-2-hydroxytoluene 0.01 Cetearyl Alcohol 14 Glyceryl stearate 1.4 Ammonium hydroxides 6.8 Ceteareth-20 3.5 octyldodecanol 1 Sodium Laureth Sulfate 0.5 1,3-butylene glycol 3.5 Sodium Cetearyl Sulfate 1.0 Oleic acid 0.1 Perfume (fragrance) 0.5 Potassium Stearate 0.5 Sodium sulphites 0.2 Tetrasodium EDTA 0.3 Carbomer 0.3 Polyquaternium-39 (ex Merquat 3330) 0.05 Potassium hydroxides 0.
  • Table 2 Composition (B) -E (amounts in% by weight) used for the process according to the invention: Paraffinum liquidum 17.00 Cetearyl Alcohol 4.00 dipicolinic 0.10 Disodium pyrophosphates 0.10 Potassium hydroxides 0.12 Etidronic Acid 0.20 PEG-40 Castor Oil 0.70 Sodium Cetearyl Sulfate 0.40 H 2 O 2 (active content) 6.00 water ad 100.00 Paraffin Liquidum 0.5 cetearyl 4.0 dipicolinic 0.1 Disodium pyrophosphates 0.1 potassium hydroxide 0.1 1,2-propylene glycol 1.0 1-Hydroxyethane-1,1-diphosphonic acid (Etidronic acid) 0.1 STEAM TRIMONIUM CHLORIDE 0.5 Ceteareth-20 1.0 H 2 O 2

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)

Claims (14)

  1. Procédé de coloration par oxydation de fibres de kératine, en particulier de cheveux, caractérisé en ce que
    a) un agent de prétraitement qui contient au moins une silicone 4-morpholinométhyle-substituée de la formule (V),
    Figure imgb0019
     dans laquelle
    A représente une unité structurelle (I), (II), (IIIa), (IIIb), (IIIe) ou (IIIf) liée par un -O-,
    Figure imgb0020
    Figure imgb0021
    Figure imgb0022
     ou représente un radical oligomère ou polymère, lié par un -O-, contenant des unités structurelles de formules (I), (II), (IIIa), (IIIb), (IIIe) et (IIIf), ou représente -OH,
    * représente une liaison à l'une des unités structurelles (I), (II), (IIIa), (IIIb), (IIIe) et (IIIf), ou représente un groupe d'extrémité B (lié par Si) ou D (lié par O),
    B représente un groupe -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3,
    D représente un groupe -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3,
    a, b et c sont des nombres entiers de 0 à 990, avec la condition a + b + c > 0
    m, n et o sont des nombres entiers de 1 à 990,
    est appliqué sur les fibres de kératine, notamment les cheveux,
    b) ensuite, pendant une durée d'une seconde à 24 heures après l'étape a) un agent de coloration capillaire est appliqué sur les fibres de kératine,
    l'agent de coloration capillaire étant obtenu par mélange d'une composition (A), qui contient au moins un précurseur de colorant par oxydation du type développeur et au moins un précurseur de colorant par oxydation du type copulateur, avec une composition (B) qui contient au moins un agent d'oxydation,
    caractérisé en ce que la composition (B) contient au moins une huile cosmétique dans une quantité totale de 10 à 80% en poids, par rapport au poids de la composition (B).
  2. Procédé selon la revendication 1, caractérisé en ce que l'agent de prétraitement, utilisé à l'étape a, contient au moins une silicone 4-morpholinométhyl-substituée de la formule (V), dans laquelle on a
    m > (n + o) ou (a + b + c) > (n + o), de préférence
    m > 8 (n + o) ou (a + b + c) > 8 (n + o), plus préférablement
    m > 25 (n + o) ou (a + b + c) > 25 (n + o), plus préférablement
    m > 77 (n + o) ou (a + b + c) > 77 (n + o), et notamment
    m > 200 (n + o) ou (a + b + c) > 200 ( n + o).
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que l'agent de prétraitement utilisé à l'étape a contient, sur la base de son poids, une ou plusieurs silicones 4-morpholinométhyl-substituées dans une quantité totale de 0,001 à 5% en poids, de préférence de 0,005 à 2% en poids, de façon particulièrement préférée de 0,01 à 1% en poids, de façon extraordinairement préférée de 0,02 à 0,1%, à chaque fois sur la base du poids total de l'agent de prétraitement.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'agent de prétraitement utilisé à l'étape a contient une ou plusieurs silicones 4-morpholinométhyl-substituées à terminaison hydroxyle, dans lesquelles le rapport molaire hydroxyle/alcoxyle est dans la gamme de 0,2:1 à 0,4:1, de préférence dans la gamme de 1:0,8 à 1:1,1.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la masse molaire moyenne en poids de la silicone 4-morpholinométhyl-substituée utilisée à l'étape a de la formule (V) est dans la gamme de 2000 à 1000000 gmol-1, de préférence dans la gamme de 5000 à 200000 gmol-1.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la silicone 4-morpholinométhyl-substituée utilisée à l'étape a de la formule (V) se présente sous la forme d'une émulsion huile-dans-eau dans laquelle la taille moyenne en nombre des particules de silicone dans l'émulsion est de préférence dans la gamme de 3 à 500 nm, de manière particulièrement préférée dans la gamme de 5 à 60 nm.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'au moins une huile cosmétique, qui est contenue dans la composition (B) dans une quantité totale de 10 à 80% en poids par rapport au poids de la composition (B), est choisie parmi les hydrocarbures naturels et synthétiques, de façon particulièrement préférée les huiles de paraffine, les isoparaffines en C18 à C30, en particulier l'isoeicosane, les polyisobutènes et les polydécènes, les isoparaffines en C8 à C16, et le 1,3-di-(2-éthylhexyl)-cyclohexane ; les esters d'alcanols en C8 à C22 linéaire ou ramifié avec de l'acide benzoïque ; les alcools gras ayant 6 à 30 atomes de carbone qui sont insaturés ou ramifiés et saturés ou ramifiés et insaturés ; les triglycérides d'acides gras en C8 à C30 linéaires ou ramifiés, saturés ou insaturés éventuellement hydroxylés, en particulier les huiles naturelles ; les esters d'alcanols C2 à C10 linéaires ou ramifiés avec l'acide dicarboxylique ; les esters des alcools gras linéaires ou ramifiés saturés ou insaturés ayant 2 à 30 atomes de carbone avec des acides gras linéaires ou ramifiés saturés ou insaturé ayant 2 à 30 atomes de carbone qui peuvent être hydroxylés ; les produits d'addition de 1 à 5 unités de propylène à des alcanols en C8 à C22 monovalent ou polyvalent ; les produits d'addition d'au moins 6 unités oxyde d'éthylène et/ou oxyde de propylène à des alcanols en C3 à C22 monovalents ou polyvalents ; les esters d'acides hydroxycarboxyliques en C2 à C7 monovalent ou polyvalent avec des alcools gras en C8 à C22 ; les esters symétriques, asymétriques ou cycliques de l'acide carbonique avec des alcanols en C3 à C22, des alcanediols en C3 à C22 ou des alcanetriols en C3 à C22 ; les esters de dimères d'acides gras en C12 à C22 insaturés (acides gras dimères) avec des alcanols en C2 à C18 linéaires, ramifiés ou cycliques monovalents ou avec des alcanols en C2 à C6 linéaires ou ramifiés polyvalents ; les huiles de silicone et des mélanges des substances susmentionnées.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que la composition (B) contient au moins une huile cosmétique dans une quantité totale de 12 à 70% en poids, de préférence de 14 à 60% en poids, de manière particulièrement préférée de 15 à 52% en poids et de manière extraordinairement préférée de 17 à 35% en poids, à chaque par rapport au poids de la composition (B).
  9. Procédé selon l'une revendications 1 à 8, caractérisé en ce que la composition (B) contient :
    de 1 à 24% en poids, de préférence de 4 à 10% en poids, de manière particulièrement préférée de 3 à 6% en poids, de peroxyde d'hydrogène (calculé sous la forme de H2O2 à 100%), en outre
    au moins une huile cosmétique dans une quantité totale de 12 à 70% en poids, de préférence de 14 à 60% en poids, de manière particulièrement préférée de 15 à 52% en poids, et de manière extraordinairement préférée de 17 à 35% en poids, en outre
    au moins un tensioactif dans une quantité totale de 0,1 à 5% en poids, de préférence de 0,5 à 3% en poids et de manière particulièrement préférée de 1 à 2% en poids, et
    au moins un alcanol saturé linéaire ayant 12 à 30 atomes de carbone dans une quantité totale de 0,1 à 10% en poids, de préférence de 0,5 à 7% en poids et de manière particulièrement préférée de 3 à 5% en poids , toutes les données en % en poids se rapportant au poids de la composition (B).
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que l'agent de coloration capillaire prêt à l'emploi utilisé à l'étape de procédé b) contient au moins une huile cosmétique dans une quantité totale de 5 à 50% en poids, de préférence de 8 à 40% en poids, de manière particulièrement préférée de 12 à 30% en poids, de manière extraordinairement préférée de 15 à 25% en poids, à chaque fois par rapport au poids de l'agent de coloration capillaire.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce qu'on laisse agir l'agent de pré traitement, appliqué à L'étape de procédé a, pendant une durée de 2 secondes à 120 minutes, de préférence de 5 secondes à 10 minutes, sur les cheveux avant d'effectuer au moins une des étapes de procédé suivantes a)i) qui sont effectuées avant l'étape de procédé b) :
    rincer les cheveux ;
    sécher les cheveux avec une serviette,
    laisser sécher les cheveux à l'air,
    sécher les cheveux au sèche-cheveux,
    sécher les cheveux au casque sèche-cheveux,
    des combinaisons des étapes de procédé susmentionnées,
    le procédé de séchage étant de préférence effectué à une température de 20°C à 150°C
  12. Procédé selon la revendication 11, caractérisé en ce qu'aucun rinçage des cheveux n'est effectué entre l'application de l'agent de prétraitement, effectuée à l'étape de procédé a, et le processus de séchage ou les processus de séchage.
  13. Procédé selon l'une des revendications 1 à 12, caractérisé en ce que la durée entre les étapes de procédé a et b est de 30 secondes à 20 minutes, de préférence de 45 secondes à 10 minutes, de manière particulièrement préférée de 1 à 5 minutes.
  14. Procédé selon l'une des revendications 1 à 13, caractérisé en ce qu'une combinaison, appliquée à l'étape b, d'au moins un précurseur de colorant par oxydation du type développeur et d'au moins un précurseur de colorant d'oxydation du type copulateur est choisie parmi au moins une des combinaisons suivantes, les composés aminés et les composés hétérocycliques azotés pouvant se présenter également sous la forme de leurs sels physiologiquement acceptables :
    p-toluènediamine/résorcinol ;
    p-toluènediamine/2-méthylrésorcinol ;
    p-toluènediamine/5-amino-2-méthylphénol ;
    p-toluènediamine/3-aminophénol ;
    p-toluènediamine/2-(2,4-diaminophénoxy)éthanol ;
    p-toluènediamine/1,3-bis(2,4-diaminophénoxy)propane ;
    p-toluènediamine/1-méthoxy-2-amino-4-(2-hydroxyéthylamino)benzène ;
    p-toluènediamine/2-amino-3-hydroxypyridine ;
    p-toluènediamine/1-naphtol ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/résorcinol ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/2-méthylrésorcinol ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/5-amino-2-méthylphénol ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/3-aminophénol ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/2-(2,4-diaminophénoxy)éthanol ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/1,3-bis(2,4-diaminophénoxy)propane ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/1-méthoxy-2-amino-4-(2-hydroxyéthylamino)benzène ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/2-amino-3-hydroxypyridine ;
    2-(2-hydroxyéthyl)-p-phénylènediamine/1-naphtol ;
    2-méthoxyméthyl-p-phénylènediamine/résorcinol ;
    2-méthoxyméthyl-p-phénylènediamine/2-méthylrésorcinol ;
    2-méthoxyméthyl-p-phénylènediamine/5-amino-2-méthylphénol ;
    2-méthoxyméthyl-p-phénylènediamine/3-aminophénol ;
    2-méthoxyméthyl-p-phénylènediamine/2-(2,4-diaminophénoxy)éthanol ;
    2-méthoxyméthyl-p-phénylènediamine/1,3-bis(2,4- diaminophénoxy)propane ;
    2-méthoxyméthyl-p-phénylènediamine/1-méthoxy-2-amino-4-(2-hydroxyéthylamino)benzène ;
    2-méthoxyméthyl-p-phénylènediamine/2-amino-3-hydroxypyridine ;
    2-méthoxyméthyl-p-phénylènediamine/1-naphtol ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/résorcinol ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/2-méthylrésorcinol ;
    N-(4-amino-3-méthylphenyl)-N-[3-(1H-imidazol-1-y)propyl]amine/5-amino-2-méthylphénol ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/3-aminophénol ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/(2-(2,4-diamino-phénoxy)-éthanol ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1,3-bis(2,4-diaminophénoxy)propane ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1-méthoxy-2-amino-4-(2-hydroxyéthylamino)benzène ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/2-amino-3-hydroxypyridine ;
    N-(4-amino-3-méthylphényl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1-naphtol ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/résorcinol ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/2-méthylrésorcinol ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/phénol/5-amino-2-méthylphénol ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/3-aminophénol ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/2-(2,4-diaminophénoxy)éthanol ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/1,3-bis(2,4-diaminophénoxy)propane ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/1-méthoxy-2-amino-4-(2-hydroxyéthylamino)benzène ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/2-amino-3-hydroxypyridine ;
    4,5-diamino-1-(2-hydroxyéthyl)pyrazole/1-naphtol.
EP13792898.2A 2012-12-19 2013-11-15 Procédé de coloration respectueux des cheveux à prétraitement au silicone et préparation d'agent oxydant renfermant de l'huile Active EP2934686B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012223809.3A DE102012223809A1 (de) 2012-12-19 2012-12-19 Haarschonendes Färbeverfahren mit Silikon-Vorbehandlung und ölhaltiger Oxidationsmittelzubereitung
PCT/EP2013/073957 WO2014095184A2 (fr) 2012-12-19 2013-11-15 Procédé de coloration respectueux des cheveux à prétraitement au silicone et préparation d'agent oxydant renfermant de l'huile

Publications (2)

Publication Number Publication Date
EP2934686A2 EP2934686A2 (fr) 2015-10-28
EP2934686B1 true EP2934686B1 (fr) 2017-09-27

Family

ID=49622813

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13792898.2A Active EP2934686B1 (fr) 2012-12-19 2013-11-15 Procédé de coloration respectueux des cheveux à prétraitement au silicone et préparation d'agent oxydant renfermant de l'huile

Country Status (4)

Country Link
US (1) US8790417B2 (fr)
EP (1) EP2934686B1 (fr)
DE (1) DE102012223809A1 (fr)
WO (1) WO2014095184A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012219583A1 (de) * 2012-10-25 2014-04-30 Henkel Ag & Co. Kgaa Haarpflegemittel mit ausgewählten aminofunktionalen Silikonen und ausgewähltem kationischen Keratinhydrolysat
DE102016225379B4 (de) * 2016-12-19 2022-03-31 Henkel Ag & Co. Kgaa Cremeförmiges Haarfärbemittel
KR101932016B1 (ko) * 2016-12-30 2018-12-26 주식회사 세화피앤씨 산화 염모제 조성물
DE102018218945A1 (de) * 2018-11-07 2020-05-07 Henkel Ag & Co. Kgaa Verfahren zur schonenden, chemischen Haarbehandlung
KR20230073178A (ko) 2020-07-21 2023-05-25 켐보 엘엘씨 디에스테르 미용 제제 및 그의 용도

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19639669A1 (de) * 1996-09-27 1998-04-02 Basf Ag Verwendung von carboxylgruppenhaltigen Polysiloxanen in kosmetischen Formulierungen
JPH11139938A (ja) * 1997-11-12 1999-05-25 Shin Etsu Chem Co Ltd 毛髪化粧料
DE19756454C1 (de) 1997-12-18 1999-06-17 Henkel Kgaa Verwendung von Glycerincarbonat
US6315989B1 (en) * 1999-12-22 2001-11-13 Revlon Consumer Products Corporation Water in oil microemulsion peroxide compositions for use in coloring hair and related methods
FR2831812B1 (fr) * 2001-11-08 2004-10-01 Oreal Utilisation de silicones aminees particulieres en pre-traitement de colorations directes ou d'oxydation de fibres keratiniques
AU2002301803B2 (en) 2001-11-08 2004-09-09 L'oreal Cosmetic compositions containing an aminosilicone and a conditioner, and uses thereof
FR2831803B1 (fr) 2001-11-08 2004-07-30 Oreal Compositions cosmetiques contenant une silicone aminee et un agent epaississant et leurs utilisations
DE102004030886A1 (de) 2004-06-25 2006-02-09 Henkel Kgaa Haarkonditionierende Mittel mit aminofunktionellen Siliconen
DE102006052729A1 (de) * 2006-11-08 2008-05-15 Wacker Chemie Ag Verfahren zur Herstellung von wässrigen Dispersionen von Organopolysiloxanen
DE102011079911A1 (de) * 2011-07-27 2013-01-31 Wacker Chemie Ag Kosmetische Zusammensetzungen
DE102011087621A1 (de) * 2011-12-02 2013-06-06 Henkel Ag & Co. Kgaa Haarbehandlungsmittel mit 4-morpholinomethyl-substuierten Silikon(en) und Verdickungsmittel(n)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
US8790417B2 (en) 2014-07-29
WO2014095184A3 (fr) 2014-12-04
DE102012223809A1 (de) 2014-06-26
WO2014095184A2 (fr) 2014-06-26
EP2934686A2 (fr) 2015-10-28
US20140165303A1 (en) 2014-06-19

Similar Documents

Publication Publication Date Title
WO2014095178A2 (fr) Agent de coloration par oxydation respectueux des cheveux contenant une composition d'agent oxydant renfermant de l'huile
EP2934472B1 (fr) Traitement des cheveux oxydatif et respectueux à prétraitement au silicone et renforçateur de décoloration
EP2934686B1 (fr) Procédé de coloration respectueux des cheveux à prétraitement au silicone et préparation d'agent oxydant renfermant de l'huile
DE102016225380A1 (de) Cremeförmiges Haarfärbemittel
WO2014095181A2 (fr) Procédé de coloration respectueux des cheveux
DE102014225221A1 (de) Oxidationsfärbemittel mit einem Dipeptid
EP2934684A2 (fr) Traitement des cheveux oxydatif et respectueux à traitement ultérieur spécial au silicone
DE102016225382A1 (de) Haarfärbemittel
EP2689773A2 (fr) Produit de teinture et de soin des cheveux avec des copolymères de silicone séquencés
WO2015090951A1 (fr) Amélioration des caractéristiques de soin de colorations capillaires grâce à l'utilisation de produits céréaliers
DE102018222222A1 (de) Oxidationsfärbemittel in Rotnuancen mit verringerter Farbverschiebung durch Kupferionen
EP3393595B1 (fr) Methode pour la coloration multiton des fibres keratiniques
WO2016139126A1 (fr) Composition de teinture d'oxydation comprenant un dipeptide et un colorant d'oxydation à base de pyrazole
WO2015090806A1 (fr) Produit de coloration d'oxydation avec substance de soin naturelle
DE102017223233A1 (de) Oxidatives Haarfärbemittel mit reduzierter Haarschädigung und verbesserten Färbeeigenschaften
WO2016139121A1 (fr) Composition de teinture d'oxydation contenant de la méthionyl-méthionine et une diamine aromatique
DE102016216866A1 (de) Oxidatives Haarfärbemittel mit optimierter Liftleistung
EP3897527A1 (fr) Colorant d'oxydation dans des nuances de rouge présentant une solidité et une homogénéité améliorées
DE102015222985A1 (de) Verbesserung der Waschechtheit
EP2689803A2 (fr) Produit de teinture et de soin des cheveux avec des copolymères séquencés
EP4168128A1 (fr) Composant d'alcalisation épaissi pour produit capillaire de coloration par oxydation
DE102015220536A1 (de) Oxidationshaarfärbemittel mit optimierter Egalisierungsleistung
EP2689804A2 (fr) Produit de teinture et de soin des cheveux avec des silicone(s) et des polymère(s)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150430

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20170216

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170504

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 931450

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171015

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013008456

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171227

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170927

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171228

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180127

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013008456

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: DE

Ref legal event code: R084

Ref document number: 502013008456

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171115

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20171130

26N No opposition filed

Effective date: 20180628

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20131115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 931450

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170927

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230531

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231123

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231120

Year of fee payment: 11

Ref country code: DE

Payment date: 20231121

Year of fee payment: 11